Constant boiling compositions of pentafluoroethane, difluoromethane, and tetrafluoroethane

ABSTRACT

Ternary mixtures of pentafluoroethane, difluoromethane and tetrafluoroethane are useful as refrigerants, aerosol propellants, heat transfer media, gaseous dielectrics, fire extinguishing agents, expansion agents for polyolefins and polyurethanes, and as power cycle working fluids.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of U.S. application Ser. No.07/628,000 filed Dec. 17, 1990, now abandoned.

FIELD OF THE INVENTION

This invention relates to constant boiling mixtures for use asrefrigerants, aerosol propellants, heat transfer media, gaseousdielectrics, fire extinguishing agents, blowing or expansion agents forpolymers such as polyolefins and polyurethanes and as power cycleworking fluids. More particularly, it relates to constant boilingmixtures of fluorinated hydrocarbons. Specifically, this inventionrelates to the use of mixtures of pentafluoroethane (HFC-125),difluoromethane (HFC-32) and tetrafluoroethane (HFC-134 and/or HFC-134a)as replacements for Refrigerant 502 (R-502), a commercial binaryazeotrope of chlorodifluoromethane (HCFC-22) and chloropentafluoroethane(CFC-115) and the like that have been used as the refrigerant innumerous commercial applications.

BACKGROUND OF THE INVENTION

Recently the long-term environmental effects of chlorofluorocarbons havecome under substantial scientific scrutiny. It has been postulated thatthese chlorine-containing materials decompose in the stratosphere, underthe influence of ultraviolet radiation, to release chlorine atoms.Chlorine atoms are theorized to undergo chemical reaction with the ozonelayer in the stratosphere. This reaction could deplete or at leastreduce the stratospheric ozone layer, thus permitting harmfulultraviolet radiation to penetrate the earth's protective ozone layer. Asubstantial reduction of the stratospheric ozone layer could have aserious deleterious impact on the quality of life on earth.

Refrigerant 502, the azeotropic mixture of about 47-50 weight percentHCFC-22 and 53-50 weight percent CFC-115 (the azeotrope is composed of48.8 weight percent HCFC-22 and 51.2 weight percent CFC-115) has longbeen used as the refrigerant in most of the country's supermarketrefrigeration cases. However, since CFC-115 is a chlorofluorocarboncompound which is being phased out by the year 2000, the industry isrequired to replace Refrigerant 502 with environmentally saferfluorinated hydrocarbons.

The tetrafluoroethanes (HFC-134 and its isomer HFC-134a) have beenmentioned as possible substitutes. However, the low vapor pressures(relatively high boiling points) limit the refrigeration capacity ofthese compounds alone, making them undesirable in R-502 applications.Also, pentafluoroethane (HFC-125) has been suggested as a replacementfor R-502, but its energy efficiency (heat removed by the evaporatordivided by the power to compress the vapor) is 10% lower than R-502.Consequently, newly designed equipment would be required to achieve therefrigeration capacity and energy efficiency currently needed for thesesupermarket applications.

Mixtures of environmentally safe materials might also be used if thedesired combination of properties could be attained in a simple (notconstant boiling) mixture. However, simple mixtures create problems inthe design and operations of the equipment used in refrigerationsystems. These problems result primarily from component separation orsegregation in the vapor and liquid phases.

Azeotropic or constant boiling mixtures of two or more components, wherethe composition of the vapor and liquid phases are substantially thesame at the temperatures and pressures encountered in the refrigerationcycle, would appear to be the answer.

It is an object of the present invention to provide a substantiallyconstant boiling composition of at least two hydrofluorocarbons that islow boiling, is non-flammable, and suitable for use as a refrigerant,aerosol propellant, a heat transfer medium, a gaseous dielectric, a fireextinguishing agent, an expansion or blowing agent for polymers and as apower cycle working fluid.

SUMMARY OF THE INVENTION

According to the present invention, a ternary fluorocarbon mixture hasbeen discovered that comprises about 5-90 weight percentpentafluoroethane, CF₃ --CHF₂, also known as HFC-125, about 5-90 weightpercent difluoromethane, CH₂ F₂, also known as HFC-32, and about 5-90weight percent tetrafluoroethane, CF₃ --CH₂ F and CHF₂ --CHF₂, alsoknown as HFC--134a and HFC 134, that is suitable for the aforementioneduses, particularly for use in the refrigeration cases found insupermarkets. The substantially constant boiling compositions compriseabout 5-59 weight percent HFC-125, 5-59 weight percent HFC-32 and about5-35 weight percent of at least one of HFC-134 and HFC-134a. The rangefor HFC-134a is anywhere from about 5-90 weight percent; and, as shownin Table 3, from 15-70 weight percent in mixtures with HFC-125 andHFC-32 were quite satisfactory. As for HFC-134, a range of about 5-45weight percent, preferably 15-45 weight percent as shown in Table 3, isquite satisfactory.

The compositions of this invention are particularly useful inrefrigeration applications since they maintain their stability and theirazeotrope-like properties at temperatures of -30° F. to 115° F. andpressures of 24 psia to 350 psia as shown in the examples hereinafter.As a matter of information, the compositions of this invention may beused successfully at temperatures as low as -50° F. to temperatures ashigh as 300° F.

The novel mixture compositions of the instant invention exhibitdifferences in dew and bubble points. However, these differences canincrease the overall energy efficiency of the refrigeration cycle and bebeneficial to refrigeration equipment designers.

There are other ternary and higher blends as shown in Table 2 havingdesirable characteristics that could be formulated by those skilled inthe art from the halocarbons defined and exemplified herein. Anotherblend that may be formulated for the purposes of this invention isHFC-125/HFC-134a/HFC-134/HFC-32.

The objective of this description is not to identify every possibleblend composition, but to illustrate our discovery of the unexpectedproperties that the ternary (or higher) blends can take on, depending onthe components and the chosen proportions.

For the purpose of this discussion, "near-azeotropic" is intended tomean essentially azeotropic or essentially constant boiling. In otherwords, included within the meaning of these terms are variable degreesof near-azeotropic behavior depending on the proportions of thecomponents. As is well recognized in this art, there is a range ofcompositions which contain the same components as the near-azeotrope anddemonstrate equivalent properties at other temperatures and pressures,but will behave essentially as those mentioned.

The novel ternary mixtures may be used to produce refrigeration bycondensing the mixtures and thereafter evaporating the condensate in thevicinity of a body to be cooled.

The novel mixtures may also be used to produce heat by condensing therefrigerant in the vicinity of the body to be heated and thereafterevaporating the refrigerant.

The use of non-azeotropic mixtures that exhibit differences in dew andbubble points can be used with countercurrent heat exchangers to offerpotential energy efficiency advantages which pure component andazeotropic and near azeotropic mixtures may not exhibit.

The novel mixtures have zero ozone depletion potentials (ODP) comparedwith Refrigerant 502. The ODP are provided in Table 1 for comparison.

The novel mixtures have little effect on the global warming potential.The global warming potentials (GWP) of the mixtures/components arelisted in Table 1 and R-502 is provided for comparison.

                  TABLE 1                                                         ______________________________________                                        Refrigant  Chemical Formula                                                                              ODP    GWP                                         ______________________________________                                        R-502      CHClF.sub.2 /CClF.sub.2 CF.sub.3                                                               .25   5.1                                         HFC-125    CHF.sub.2 CF.sub.3                                                                            .0     .65                                         HFC-134a   CF.sub.3 CH.sub.2 F                                                                           .0     .29                                         HFC-134    CHF.sub.2 CHF.sub.2                                                                           .0     .15                                         HFC-32     CH.sub.2 F.sub.2                                                                              .0     .15                                         ______________________________________                                    

Also, the mixtures can be formulated such that the initial compositionor the composition during leakage remains nonflammable. By"nonflammable" is meant a gas mixture in air which will not burn whensubjected to a spark igniter according to Flammability Test MethodASTM-E681-85.

It should be understood that one or more of the compounds shown in Table2 can be substituted or combined with the substantially constant boilingternary mixtures of this invention to provide additional substantiallyconstant boiling mixtures for similar uses while adding advantageousproperties unique to the added component(s).

                  TABLE 2                                                         ______________________________________                                        Nomenclature       Chemical Formula                                           ______________________________________                                        HFC-22             CHClF.sub.2                                                HFC-143a           CH.sub.3 CF.sub.3                                          HFC-161            CH.sub.2 FCH.sub.3                                         FC-218             CF.sub.3 CF.sub.2 CF.sub.3                                 Propane            CH.sub.3 CH.sub.2 CH.sub.3                                 HFC-23             CHF.sub.3                                                  HFC-227ea          CF.sub.3 CHFCF.sub.3                                       ______________________________________                                    

The invention will be more clearly understood by referring to theexamples which follow.

EXAMPLES 1-12

Evaluation of the refrigeration properties of the novel ternary mixturesof the invention versus Refrigerant 502 are shown in Table 3. The datawere generated on a one-ton basis, i.e., based on the removal of heatfrom a space at the rate of 12,000 BTU/hr.

                                      TABLE 3                                     __________________________________________________________________________    Comparison of Refrigeration Performance                                              Conditions                                                                    Evaporator                                                                              Condenser     Net                                                   Temp.     Temp.         Refrig.                                               In Out                                                                              Pres.                                                                             In Out                                                                              Pres.   Effect                                         Refrigerants                                                                         (°F.)                                                                     (°F.)                                                                     (psia)                                                                            (°F.)                                                                     (°F.)                                                                     (psia)                                                                            C.O.P.                                                                            (BTU/lb)                                                                            Example                                  __________________________________________________________________________    R-502  -30                                                                              -30                                                                              24.0                                                                              115                                                                              115                                                                              281.9                                                                             1.89                                                                              46.7  Control                                  Mixtures                                                                      125/134a/32                                                                   (wt. %)                                                                       45/45/10                                                                             -34                                                                              -25                                                                              18.5                                                                              119                                                                              112                                                                              264.3                                                                             1.93                                                                              68.5  1                                        75/15/10                                                                             -32                                                                              -28                                                                              24.5                                                                              117                                                                              113                                                                              318.3                                                                             1.80                                                                              50.0  2                                        18/57/25                                                                             -36                                                                              -25                                                                              18.6                                                                              120                                                                              111                                                                              270.1                                                                             1.97                                                                              73.2  3                                        25/25/50                                                                             -34                                                                              -27                                                                              26.6                                                                              117                                                                              112                                                                              350.3                                                                             1.86                                                                              81.7  4                                        50/30/10                                                                             -34                                                                              -26                                                                              21.1                                                                              118                                                                              112                                                                              286.9                                                                             1.87                                                                              74.2  5                                        10/70/20                                                                             -36                                                                              -25                                                                              16.9                                                                              120                                                                              111                                                                              244.5                                                                             2.01                                                                              73.1  6                                        Mixtures                                                                      125/134/32                                                                    (wt. %)                                                                       45/45/10                                                                             -38                                                                              -23                                                                              16.5                                                                              121                                                                              109                                                                              250.1                                                                             1.95                                                                              61.7  7                                        75/15/10                                                                             -33                                                                              -27                                                                              24.0                                                                              117                                                                              113                                                                              315.7                                                                             1.80                                                                              50.8  8                                        18/57/25                                                                             -39                                                                              -21                                                                              16.0                                                                              123                                                                              108                                                                              246.7                                                                             2.01                                                                              77.9  9                                        25/25/50                                                                             -36                                                                              -25                                                                              24.5                                                                              119                                                                              111                                                                              337.9                                                                             1.87                                                                              84.2  10                                       50/30/10                                                                             -36                                                                              -25                                                                              19.7                                                                              119                                                                              111                                                                              281.7                                                                             1.87                                                                              56.1  11                                       10/70/20                                                                             -39                                                                              -21                                                                              13.6                                                                              123                                                                              108                                                                              216.8                                                                             2.07                                                                              78.8  12                                       __________________________________________________________________________

"Coefficient of Performance" (COP) is the ratio of net refrigerationeffect to the compressor work. It is a measure of refrigerant energyefficiency.

"Net Refrigeration Effect" is the change in enthalpy of the refrigerantin the evaporator, i.e., the heat removed by the refrigerant in theevaporator.

For a refrigeration cycle typified by the above conditions, the COP ofthe mixtures are either significantly higher or essentially the same asR-502. These mixtures exhibit temperature glides (difference in inletand exit temperature) through the condenser and evaporator. These glidesin temperature vary from 3° to 18° F., depending on the composition ofthe mixture. In the case of an azeotrope the temperature glide is 0, inthe case of a near-azeotropic mixture a temperature glide may be as muchas 10° F. However, these temperature glides should not pose anysignificant problems to equipment manufacturers. In fact, highertemperature glides may be useful to aid designers increase the energyefficiency of their machines. Also, the mixtures have much more capacitythan R-502, due to their higher vapor pressures.

Additives such as lubricants, corrosion inhibitors, stabilizers, dyesand other appropriate materials may be added to the novel compositionsof the invention for a variety of purposes provided they do not have anadverse influence on the composition for their intended applications.

In addition to refrigeration applications, the novel constant boilingcompositions of the invention are also useful as: aerosol propellants,heat transfer media, gaseous dielectrics, fire extinguishing agents,expansion agents for polymers such as polyolefins and polyurethanes, andpower cycle working fluids.

EXAMPLE 13

A phase study was made on pentafluoroethane, tetrafluoroethane anddifluoromethane to verify the fractionation and change in vapor pressureduring a phase change from liquid to vapor.

Blends were prepared in 75 cc stainless steel cylinders consisting ofpentafluoroethane, 1,1,1,2-tetrafluoroethane, and difluoromethane. Thecylinders were agitated with a magnetic stirrer and submerged in aconstant temperature bath at 23.8° C. The vapor pressure was constantlymeasured using a pressure transducer and the vapor composition wassampled at various times during the experiment and analyzed using astandard gas chromatography method. Initial and final liquidconcentrations were also analyzed by gas chromatography. Initial liquid(IQ), final liquid (FQ), vapor composition and vapor pressure datarecorded in Tables 4, 5 and 6.

                  TABLE 4                                                         ______________________________________                                        Per-                        Vapor Pressure                                    Sam- cent   Composition (wt. %)       (%                                      ple  Loss   HFC-125  HFC-134a                                                                              HFC-32 (psia)                                                                              Change)                             ______________________________________                                        IQ   0      48.8     17.3    33.9   207.2 0                                   1    6.3    51.0     4.3     44.6   206.0 0.6                                 2    12.5   51.8     7.1     41.1   204.8 1.2                                 3    18.8   50.9     8.6     40.5   203.6 1.7                                 4    25.0   50.9     9.5     39.7   202.2 2.4                                 5    31.3   50.6     10.7    38.7   200.5 3.2                                 6    37.5   50.6     11.2    38.1   198.5 4.2                                 7    43.8   50.6     12.0    37.5   196.5 5.2                                 8    50.4   50.6     12.2    37.2   193.7 6.5                                 FQ   50.4   49.4     22.0    28.6   193.7 6.5                                 ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                        Per-                        Vapor Pressure                                    Sam- cent   Composition (wt. %)       (%                                      ple  Loss   HFC-125  HFC-134a                                                                              HFC-32 (psia)                                                                              Change)                             ______________________________________                                        IQ   0      33.9     38.2    27.9   188.4 0                                   1    8.3    41.2     18.8    39.5   184.1 2.3                                 2    16.7   40.9     21.9    37.3   180.8 4.0                                 3    25.0   40.2     24.0    35.7   178.3 5.4                                 4    33.0   38.9     25.3    35.0   174.0 7.6                                 5    41.8   37.4     30.3    32.3   171.2 9.1                                 6    51.0   37.3     32.5    30.2   168.7 10.4                                FQ   51.0   30.2     47.0    22.7   168.7 10.4                                ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                        Per-                        Vapor Pressure                                    Sam- cent   Composition (wt. %)       (%                                      ple  Loss   HFC-125  HFC-134a                                                                              HFC-32 (psia)                                                                              Change)                             ______________________________________                                        IQ   0      18.7     56.4    24.8   173.2 0                                   1    1.7    26.5     36.9    36.6   172.1 0.4                                 2    6.2    25.5     37.5    37.0   169.7 1.4                                 3    10.6   25.3     38.5    36.2   164.5 2.4                                 4    15.1   24.8     40.2    35.5   162.5 3.5                                 5    19.6   24.2     41.6    34.3   160.1 4.5                                 6    24.4   24.4     40.9    34.6   158.4 5.7                                 7    28.9   23.8     42.8    31.3   155.6 7.1                                 8    33.3   22.8     45.9    31.3   154.0 8.4                                 9    37.8   23.1     45.7    31.2   151.3 9.8                                 10   42.2   23.4     46.3    31.6   149.0 11.2                                11   46.7   20.8     49.7    29.5   146.3 12.8                                12   48.9   21.1     51.8    27.1   144.1 13.8                                13   54.4   21.4     51.3    27.3   140.2 15.8                                FQ   54.4   12.7     73.1    14.2   140.2 15.8                                ______________________________________                                    

These data (Tables 4-6) demonstrate that with more than 50% of theoriginal charge depleted, the vapor pressure has changed less than 16%in all cases. The degree of fractionation depends on thetetrafluoroethane concentration and can be adjusted to give smallchanges in vapor pressure. Mixtures containing 35 wt. % of1,1,1,2-tetrafluoroethane (HFC-134a) or less are consideredsubstantially constant boiling since the vapor pressure will change lessthan 10% at 50% leakage. Mixtures containing greater than 35 wt. % of1,1,1,2-tetrafluoroethane are considered non-azeotropic as the vaporpressure has changed more than 10% at 50% leakage. These mixtures couldstill be quite useful in many applications, especially those thatrequire very small sizes. At small charge sizes, recharging the mixturedue to vapor leakage to return to the desired composition does not poseany significant problem. Substituting 1,1,2,2-tetrafluoroethane(HFC-134) for HFC-134a would be expected to give similar results atlower HFC-134 concentrations.

These data also demonstrate that, even though the mixtures fractionateand the vapor pressure decreases, the difluoromethane concentration inboth the liquid and vapor phases during leakage also decreases.Therefore, the blend will not become flammable if the initialconcentration is nonflammable. Similar behavior is predicted for themixture containing HFC-134 instead of HFC-134a.

EXAMPLE 14

The ozone depletion potential is based on the ratio of calculated ozonedepletion in the stratosphere resulting from the emission of a compoundcompared to the ozone depletion potential resulting from the same ratioof emission of CFC-11 which is set at 1.0. A method of calculating ozonedepletion potential is described in "The Relative Efficiency of a Numberof Halocarbons for Destroying Stratospheric Ozone", by D. J. Wuebbles,Lawrence Livermore Laboratory Report UCID-18924, January, 1981, and"Chlorocarbon Emission Scenarios: Potential Impact on StratosphericOzone", by D. J. Wuebbles, Journal Geophysics Research, 88,1433-1443,1983.

HFC-125 (CF₃ CF₂ H), HFC-134a (CF₃ CFH₂) or HFC-134 (CF₂ HCF₂ H), andHFC-32 (CF₂ H₂) contain no chlorine atoms; therefore, they have no ozonedepletion potential (0 ODP).

The global warming potentials (GWP) of the fluorocarbons were determinedusing the method described in the "Scientific Assessment ofStratospheric Ozone: 1989", sponsored by the U.N. Environment Programme.The GWP is a phenomenon that occurs in the stratosphere. It iscalculated using a model that incorporates parameters based on theagent's atmospheric lifetime and its infra-red cross-section or itsinfra-red absorption strength per mole as measured with an infra-redspectrophotometer.

I claim:
 1. A substantially constant boiling mixture consistingessentially of a ternary mixture of 5-59 weight percentpentafluoroethane, 5-59 weight percent difluoromethane and 5-35 weightpercent 1,1,1,2-tetrafluoroethane having a vapor pressure of about 169to about 207 psia. at 23.8° C. and wherein the vapor pressure changesless than about 10% after leakage of 50% of the initial mixture.
 2. Aprocess for producing refrigeration consisting essentially of the stepsof condensing the mixture of claim 1 and, thereafter, evaporating saidmixture in the vicinity of the body to be cooled.